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Decarboxylation and Decarboxylation Radical Addition of Alkyl Carboxylates of Photoactivated Electron Donor-Acceptor Complexes

An electron donor and addition reaction technology, which is applied in the field of decarboxylation of alkyl carboxylate and decarboxylation Giese radical addition reaction, can solve the problems of reducing economic benefits of production, hidden dangers of product safety, and increasing raw material costs, so as to reduce expensive Raw material input, the effect of improving purity and safety, and reducing the output of by-products

Active Publication Date: 2022-07-12
HAINAN NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the catalysts used for the above purposes are often expensive, which greatly increases the cost of raw materials in production and reduces the economic benefits of production.
In addition, the catalyst mixed in the target product is often highly toxic and difficult to separate from the target product. The manufacturer must invest a lot of technical costs in order to separate the catalyst in the target product. At the same time, the remaining catalyst in the target product that cannot be separated It will also reduce the purity of the target product and affect the quality of the product
For example, the decarboxylation product obtained by the Barton decarboxylation reaction is inevitably mixed with tin compounds and mercaptans. These substances have high toxicity and pungent odor, which introduce safety hazards to the product. The cost of separating these substances from the product Occupies a large proportion of the product output cost

Method used

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  • Decarboxylation and Decarboxylation Radical Addition of Alkyl Carboxylates of Photoactivated Electron Donor-Acceptor Complexes
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  • Decarboxylation and Decarboxylation Radical Addition of Alkyl Carboxylates of Photoactivated Electron Donor-Acceptor Complexes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Example 1 Free radical clock experiment

[0054] 1. Main medicines needed

[0055] Dichloromethane (DCM), N,N-dimethylacetamide (DMA).

[0056] 2. Data collection

[0057] Thin Layer Chromatography (TLC), Gas Chromatography-Mass Spectrometry (GC-MS), Nuclear Magnetic Resonance Spectrometry (NMR)

[0058] 3. Reaction steps of the free radical clock experiment

[0059] 3.1 Drop into a Schlenk tube equipped with a stirrer (1.0 equiv, 0.2 mmol), (0.3 mmol), HE (0.3 mmol), tetramethylpiperidine nitroxide (TEMPO) (2.0 equiv, 0.4 mmol), evacuated the original gas in the tube and passed argon to fill the tube space (repeat 3 times) . Under an argon atmosphere, anhydrous DMA (2.0 mL) was injected into the reaction system. The reaction system was illuminated with 40 W of blue (456 nm) LED illumination at room temperature while stirring the mixture in the reaction system continuously for 12 h. The resulting mixture was quenched with saturated NaCl solution and suction fi...

Embodiment 2

[0066] Example 2 Gram-scale experiment

[0067] In this example, the experiment carried out in Section 3.2 of Example 1 is scaled up to a gram-scale experiment. Drop into Schlenk tube with stirrer (6 mmol), (9 mmol), HE (9 mmol), evacuated the original gas in the tube and passed argon to fill the tube space (repeated 3 times). Under an argon atmosphere, anhydrous DMA (50 mL) was injected into the reaction system. The reaction system was illuminated with 40 W of blue (456 nm) LED illumination at room temperature while stirring the mixture in the reaction system continuously for 12 h. After the reaction, the obtained mixture was quenched with saturated NaCl solution, and then subjected to suction filtration with 50 mL of ethyl acetate, and the suction filtration was repeated 3 times. The product was separated by flash column chromatography on a silica gel plate, and the eluent used was: petroleum ether / ethyl acetate=10 / 1.

[0068] The reactant reaction conditions and the ...

Embodiment 3

[0072] 1. Experiment setup method

[0073] 1.1 The HE and RAE (ie, ) according to the reaction concentration in Example 1 to prepare the DMA solution of HE, the DMA solution of RAE and the DMA solution of HE+RAE (c=c*), and take part of the DMA solution of HE+RAE (c=c*) to dilute 10 times to obtain a DMA solution of HE+RAE (c=0.1c*).

[0074] 1.2 The HE and RAE (ie, ) according to the reaction concentration in Example 1 to prepare HE DCM solution, RAE DCM solution and HE+RAE DCM solution (c=c*), and take part of HE+RAE DCM solution (c=c*) to dilute 10 times to obtain HE+RAE in DCM (c=0.1 c*).

[0075] 2. Data acquisition method

[0076] The absorption spectrum of the above solution was tested using a UV-Vis absorption spectrometer.

[0077] 3. Test results

[0078] Test results such as figure 1 and figure 2 shown. like figure 1 As shown, the absorption spectrum peaks of HE+RAE in DMA solution (c=c*) with HE and RAE dissolved in DMA simultaneously to simulate the r...

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Abstract

Decarboxylation and Decarboxylation Giese Radical Addition of Alkyl Carboxylates of a Photoactivated Electron Donor-Acceptor Complex: Irradiation of Hans Ester and Blue-violet Light in the Wavelength Range of 370–470 nm in a Solution Environment The reaction was carried out under an inert protective atmosphere at an equivalence ratio of 1:1–3:1–2. The photoactivated hans esters are converted into free radicals, which can undergo decarboxylation without catalyst under the attack of free radicals, and undergo Giese radical addition reactions with compounds containing alkenyl groups.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and in particular relates to a decarboxylation and decarboxylation Giese radical addition reaction of an alkyl carboxylate of a photoactivated electron donor-acceptor complex. Background technique [0002] Aliphatic carboxylic acids have excellent properties such as easy operation, abundant products, and environmental friendliness, and can be widely used in green chemical synthesis. Based on this, decarboxylation and decarboxylation Giese radical addition reactions of alkyl carboxylates using aliphatic carboxylic acids as reactants have been intensively developed. At present, the method mainly used to promote the decarboxylation of carboxylate to form a carbon-carbon bond structure is mainly: using a transition metal complex as a catalyst under high temperature reaction conditions to catalyze the reaction of the reactants. However, the catalysts used for the above purposes are often expensive, w...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/343C07C69/533C07C69/63C07C69/606C07C69/65C07C69/608C07C69/712C07C69/24C07D211/34
CPCC07C67/343C07D211/34C07C2601/14C07C2601/08C07C69/533C07C69/63C07C69/606C07C69/65C07C69/608C07C69/712C07C69/24Y02P20/584
Inventor 郑超陈光英宋小平李小宝
Owner HAINAN NORMAL UNIV
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